Cyano-substituted sulfur-containing compounds, and compositions containing same and organoleptic uses thereof

ABSTRACT

Described are cyano-substituted sulfur-containing compounds defined according to a structure selected from the group consisting of: ##STR1## wherein M is an alkali metal as well as uses of the nonionic structures of said group for their organoleptic properties.

This application is a continuation-in-part of application for U.S.Letters Patent, Ser. No. 273,016 filed on Nov. 18, 1988, now U.S. Pat.No. 4,883,884 issued on Nov. 28, 1989.

BACKGROUND OF THE INVENTION

This invention relates to hydroxyl-and-cyano-substitutedsulfur-containing compounds having the structures: ##STR2## (wherein Mis alkali metal) and compositions containing same produced by reactionof thioacetic acid with either (i) geranonitrile in the form of eitherthe mixture of compounds having the structures: ##STR3## or the singlecompound having the structure: ##STR4## or (ii) dihydro linalool havingthe structure: ##STR5## and uses a subgenus thereof having thestructures: ##STR6## as well as products produced according to theforegoing processes in augmenting or enhancing the aroma or taste ofconsumable materials including perfume compositions, colognes, perfumedarticles, foodstuffs and chewing gums.

There has been considerable work performed relating to substances whichcan be used to impart (or alter, modify or enhance) fragrances andaromas and/or tastes to (or in) perfume compositions, colognes, perfumedarticles, foodstuffs and chewing gums. These substances are used todiminish the use of natural materials, some of which may be in shortsupply and/or to provide more uniform properties in the finishedproduct.

Powerful, long-lasting, green, floral, rose, natural buchu leaf, tomatoleaf, herbaceous, basil, minty and grapefruit-like aromas with natural"ontiga", tomato leaf, minty and grapefruit-like undertones are highlydesirable to many types of perfume compositions, perfumes and perfumedarticles, particularly herbal fragrances and herbal fragranced soaps anddetergents.

Grapefruit and nootkatone-like aroma and taste nuances are highlydesirable in the creation of flavors for foodstuffs and chewing gums.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product of Example I(A)containing the compound having the structure: ##STR7##

FIG. 2 is the GLC profile for fraction 6 of the distillation of thereaction product of Example I(A) containing the compound having thestructure: ##STR8## (Conditions: SE-30 column programmed at 100°-220° C.at 8° C. per minute).

FIG. 3 is the NMR spectrum for the compound having the structure:##STR9## prepared according to Example I(A).

FIG. 4 is the infra-red spectrum for the compound having the structure:##STR10## prepared according to Example I(A).

FIG. 5 is the GLC profile of the base-washed (NaHCO₃) crude reactionproduct of Example I(B) containing compounds having the structures:##STR11##

FIG. 6 is the GLC profile of the water-washed crude reaction product ofExample I(B) containing compounds having the structures: ##STR12##

FIG. 7 is the GLC profile for the crude reaction product of Example IIcontaining the compound having the structure: ##STR13## (Conditions:SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 8 is the GLC profile for fraction 4 of the distillation of thereaction product of Example II containing the compound having thestructure: ##STR14## (Conditions: SE-30 column programmed at 100°-220°C. at 16° C. per minute).

FIG. 9 is the NMR spectrum for the compound having the structure:##STR15##

FIG. 10 is the infra-red spectrum for the compound having the structure:##STR16##

FIG. 11 is a cut-away side elevation view of apparatus used in preparingthe fragrance containing polymers of our invention.

FIG. 12 is a cross sectional view taken along lines 12--12 of FIG. 11.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product of Example I(A)containing the compound having the structure: ##STR17## The peakindicated by reference numeral 10 is the peak for the compound havingthe structure: ##STR18##

FIG. 2 is the GLC profile for fraction 6 of the distillation of thereaction product of Example I(A). (Conditions: SE-30 column programmedat 100°-220° C. at 8° C. per minute). The peak indicated by referencenumeral 20 is the peak for the compound having the structure: ##STR19##

FIG. 5 is the GLC profile for the base-washed crude reaction product ofExample I(B) (washed with sodium bicarbonate). The peaks indicated byreference numeral 150 are the peaks for the compounds having thestructures: ##STR20## The peak indicated by reference numeral 152 is thepeak for the compound having the structure: ##STR21## The peaksindicated by reference numeral 153 are the peaks for the compoundshaving the structures: ##STR22## The peaks indicated by referencenumeral 154 is the peak for the compound having the structure: ##STR23##

FIG. 6 is the GLC profile for the crude water-washed reaction product ofExample I(B). The peaks indicated by reference numeral 160 are the peaksfor the compounds having the structures: ##STR24## The peak indicated byreference numeral 162 is the peak for the compound having the structure:##STR25## The peaks indicated by reference numeral 163 are the peaks forthe compounds having the structures: ##STR26## The peak indicated byreference numeral 164 is the peak for the compound having the structure:##STR27##

FIG. 7 is the GLC profile for the crude reaction product of Example II.The peak indicated by reference numeral 50 is the peak for the compoundhaving the structure: ##STR28##

FIG. 8 is the GLC profile for fraction 4 of the distillation of thereaction product of Example II. The peak indicated by reference numeral60 is the peak for the compound having the structure: ##STR29##

Referring to FIGS. 11 and 12, a thermoplastic polymer, e.g.,polyethylene is heated to about 220°-250° C. in a container 212 of thekind illustrated in FIGS. 11 and 12. A formulation containing of atleast one of the organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention having one of thestructures: ##STR30## is then quickly added to the liquifiedthermoplastic polymer. The lid 228 is put in place and the agitatingmeans 273 is actuated. The temperature is maintained at about 225° F.and the mixing is continuous for about 5-15 minutes. The valve "V" isthen opened to allow flow of the molten thermoplastic polymer enrichedwith the fragrance containing at least one of the organolepticallyuseful hydroxyl-and-cyano-substituted sulfur containing compounds of ourinvention to exit through the orifices 234. The liquid falling throughthe orifices 234 solidifies almost instantaneously upon impact with themoving cooled conveyor 238. The thermoplastic polymer beads or pellets224 having pronounced aromas which are aesthetically pleasing are thusformed.

The conveyor 238 is moved using conveyor rollers 240 and 242. The vessel212 is heated using heating coils 212A using power input suppliesindicated by reference numerals 214, 216, 224, 222, 220 and 226. Thesolidified beads containing fragrance containing the at least one of theorganoleptically useful hydroxyl-and-cyano-substituted sulfur-containingcompounds of our invention are indicated by 244 traveling into container245 where they are used for subsequent processing. The conveyor iscooled using a cooling device indicated by reference numerals 248, 256,215 and 254.

THE INVENTION

The invention relates to hydroxyl-and-cyano-substitutedsulfur-containing compounds defined according to the structures:##STR31## (wherein M is alkali metal), processes for preparing same,products produced by said processes as well as organoleptic uses of saidproducts produced by said processes as well as the subgenus of compoundshaving the structures: ##STR32## in augmenting or enhancing the aroma oftaste of consumable materials.

Such consumable materials are perfume compositions, perfumed articles,perfumes, colognes, foodstuffs and chewing gums.

This invention also relates to the process for preparing the compoundshaving the structures: ##STR33## (wherein M is alkali metal) by means ofreacting geranonitrile, either in the form of a mixture of compoundshaving the structures: ##STR34## or (ii) in the form of the singlecompound having the structure: ##STR35## with thioacetic acid accordingto one of the following two reaction sequences: ##STR36## are carriedout at a temperature of 60°-80° C. over a period of between about 1 andabout 5 hours. The mole ratio of geranonitrile, either (a) the mixtureof compounds having the structure: ##STR37## or the single compoundhaving the structure: ##STR38## to thioacetic acid is between about1:0.5 and about 0.5:1 with a slight excess of mixture of compoundshaving the structures: ##STR39## or the single compound having thestructure: ##STR40## to thioacetic acid being preferred (e.g., 3:2.5).

At the end of the reaction, the reaction products having the structures:##STR41## are washed with base (e.g., sodium bicarbonate, sodiumhydroxide, potassium hydroxide or lithium hydroxide) giving rise to thefollowing reactions: ##STR42##

The compounds thus produced having the structures: ##STR43## (wherein Mrepresents alkali metal) on treatment with water according to one of thereactions: ##STR44## give rise to production of the compounds having thestructures: ##STR45##

These compounds may be used "as is" for their organoleptic properties orthe compounds having the structures: ##STR46## may be cyclized on heattreatment (e.g., during distillation) according to the reaction:##STR47## causing the compound having the structure: ##STR48## to berecovered which may be also shown as having the structure: ##STR49##

The compound having the structure: ##STR50## distills at 108° C. and 3mm/Hg. pressure.

The compounds having the structures: ##STR51## each having a naturalbuchu leaf, tomato leaf, herbaceous, basil, minty and grapefruit-likearoma with natural "ontiga", tomato leaf, minty and grapefruit-likeundertones from a fragrance standpoint. From a flavor standpoint thecompounds having the structures: ##STR52## each has a green, minty,grapefruit-like and nootkatone aroma and taste profile.

The compounds having the structures: ##STR53## each have intensities andsubstantivities at least twofold (2×) that of the compound having thestructure: ##STR54##

This invention also relates to a process for preparing theS(4-hydoxy-1-isopropyl-4-methylhexyl) thioacetate having the structure:##STR55## by reacting thioacetic acid having the structure: ##STR56##with dihydrolinalool having the structure: ##STR57## according to thereaction: ##STR58##

The reaction is carried out at a temperature in the range of from about65° C. up to about 95° C. for a period of time of from about one hour upto about five hours. The mole ratio of dihydrolinalool having thestructure: ##STR59## to thioacetic acid having the structure: ##STR60##may range from about 0.5:1.5 up to about 1.5:0.5 with a preferred moleratio of about 3.0 moles dihydrolinalool to 2.5 moles thioacetic acid.

The compound having the structure: ##STR61## has a green, floral androse aroma profile.

Table I set forth below indicates the organoleptic properties ofmaterials produced according to the processes of our invention:

                  TABLE I                                                         ______________________________________                                        Structure of Hydroxyl-and-                                                    Cyano-Substituted Sulfur-                                                                      Organoleptic                                                 Containing Compound:                                                                           Properties                                                   ______________________________________                                        Tetrahydro-5-isopropyl-2-                                                                      A natural buchu leaf, tomato                                 methyl-2-thiophene aceto-                                                                      leaf, herbaceous, basil,                                     nitrile having the structure:                                                                  minty and grapefruit-like                                     ##STR62##       aroma profile with natural "ontiga", tomato leaf, minty                       and grapegruit-like undertones.                              produced according                                                            to Example I.                                                                 The compound having                                                                            A natural buchu leaf, tomato                                 the structure:   leaf, herbaceous, basil,                                      ##STR63##       minty and grapefruit-like aroma profile with natural                          "ontiga", tomato leaf, minty and grapefruit-like                              undertones having an intensity and substantivity twofold                      that of the compound having the structure:                                     ##STR64##                                                                    produced according to                                                         Example I.                                                   The compound having                                                                            A natural buchu leaf, tomato                                 the structure:   leaf, herbaceous, basil,                                      ##STR65##       minty and grapefruit-like aroma profile with natural                          "ontiga", tomato leaf, minty and grapefruit-like                              undertones having and intensity and substantivity                             twofold that of the compound having the structure:                             ##STR66##                                                                    produced according                                                            to Example I.                                                The compound having                                                                            A natural buchu leaf, tomato                                 the structure:   leaf, herbaceous, basil,                                      ##STR67##       minty and grapefruit-like aroma profile with natural                          "ontiga", tomato leaf, minty and grapefruit-like                              undertones having an intensity and substantivity two                          fold that of the compound having the structure:                                ##STR68##                                                                    produced according                                                            to Example I.                                                The compound having                                                                            A natural buchu leaf, tomato                                 the structure:   leaf, herbaceous, basil,                                      ##STR69##       minty and grapefruit-like aroma profile with natural                          "ontiga", tomato leaf, minty and grapefruit-like                              undertones having an intensity and substantivity twofold                      that of the compound having the structure:                                     ##STR70##                                                                    produced according                                                            to Example I.                                                The compound having                                                                            A green, floral and rose aroma                               the structure:   profile.                                                      ##STR71##                                                                    prepared according                                                            to Example II.                                                                ______________________________________                                    

The organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention having the structure:##STR72## are useful as olfactory agents and can be incorporated into awide variety of compositions each of which will be enhanced or augmentedby their natural green, floral, rose, buchu leaf, tomato leaf,herbaceous, basil, minty and grapefruit-like aromas with natural tomatoleaf, minty and grapefruit-like undertones.

The organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention can be added to perfumecompositions as pure compounds or they can be added to mixtures ofmaterials in fragrance imparting compositions to provide a desiredfragrance character to a finished perfume material.

The perfume and fragrance compositions obtained according to thisinvention are suitable in a wide variety of perfumed articles and canalso be used to enhance, modify or reinforce natural fragrancematerials. It will thus be appreciated that the organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention is useful as an olfactory agent and fragrance.

The term "perfume composition" is used herein to mean a mixture ofcompounds including, for example, natural essential oils, syntheticessential oils, alcohols, aldehydes, ketones, esters, lactones, nitriles(other than the nitrile of our invention) and frequently hydrocarbonswhich are admixed so that the combined odors of the individualcomponents produce a pleasant or desired fragrance. Such perfumecompositions usually contain (a) the main note or "bouquet" orfoundation stone of the composition, (b) modifiers which round off andaccompany the main note, (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaporation and (d) topnoteswhich are usually low-boiling, fresh-smelling materials. Such perfumecompositions of our invention can be used in conjunction with carriers,vehicles, solvents, dispersants, emulsifiers, surface active agents,aerosol propellants and the like.

In perfume compositions, the olfactory components contribute theirparticular olfactory characteristics but the overall effect of theperfume composition will be the sum of the effect of each ingredient.This, the organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention can be used to alter,augment, modify or enhance the aroma characteristics of a perfumecomposition or a perfumed article, for example, by highlighting ormoderating the olfactory reaction contributed by another ingredient ofthe composition.

The amount of the organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention which will be effective inperfume compositions depends upon many factors including the otheringredients, the amounts and the effects which are desired. It has beenfound that perfume compositions containing as much as 40% or as littleas 0.005% by weight of the organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of thisinvention, or even less, can be used to impart a powerful, long-lasting,green, floral, rose, natural buchu leaf, tomato leaf, herbaceous, basil,minty and grapefruit-like aroma with natural "ontiga" tomato leaf, mintyand grapefruit-like undertones to soaps, cosmetics and other products.The amount employed will depend upon considerations of cost, nature ofthe end product, the effect desired in the finished product andparticular fragrance sought.

The organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention as disclosed herein can beused alone in a fragrance modifying composition or in a perfumecomposition as an olfactory component in detergents (e.g., anionic,cationic, nonionic or zwitterionic solid or liquid detergents, andsoaps, space deodorants; perfumed plastics; perfume compositions;colognes, bath preparations such as bath oils, bath salts; hairpreparations such as lacquers, brilliantines, pomades and shampoos;fabric softener compositions, fabric softener articles such as BOUNCE®(manufactured by the Procter & Gamble Company of Cincinnati, Ohio),cosmetic preparations such as creams, powders, deodorants, hand lotions,sun screens, powders such as talcs, dusting powders, face powders andthe like. When the organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention is used in perfumed articles such as the foregoing, it can beused in amounts of 0.01% or lower and generally it is preferred not touse more than about 2% in the finished perfumed article since the use oftoo much will tend to unbalance the total aroma and will needlesslyraise the cost of the article. Thus, in summary, in perfumed articles,the organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds may be used in the range of from about 0.01%up to about 2.0%.

When the organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention are used as food flavoradjuvants are used as food flavor adjuvants, or is used to augment orenhance the flavor or aroma characteristics of foodstuffs, the nature ofthe co-ingredients included with said organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention in formulating the product composition will also to augmentthe organoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein in regard to flavors, the term "augment" in its variousforms means "supplying or imparting flavor, character or note tootherwise bland, relatively tasteless substances or augmenting theexisting flavor characteristics wherein natural flavor is deficient insome regard or supplementing the existing flavor impression to modifyits quality, character or taste".

As used herein in regard to food flavors, the term "enhance" is used tomean the intensification of a flavor or aroma characteristic or notewithout the modification of the quality thereof. Thus "enhancement" of aflavor or aroma means that the enhancement agent does not add anyadditional flavor note.

As used herein the term "foodstuff" includes both solids and liquids andingestible materials or chewable but non-ingestible materials such aschewing gum. Such materials usually do, but need not have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,gelatin desserts, dairy products, candies, vegetables, cereals, softdrinks, snacks and the like.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. Apart from the requirements thatany such materials be organoleptically compatible with theorganoleptically useful hydroxyl-and-cyano-substituted sulfur-containingcompounds of our invention, they should also be non-reactive with theorganoleptically useful hydroxyl-and-cyano-substituted sulfur-containingcompounds of our invention and "ingestibly acceptable" and thus,non-toxic or otherwise non-deleterious. Accordingly, such materialswhich may in general be characterized as flavoring adjuvants or vehiclescomprise broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride,antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2 and 3tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skin milk powder, hexoses, pentoses,disaccharides, e.g., sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methylbutyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl,beta,beta-dimethylacrolein, n-hexanal, 2-hexenal, cis-3-hexenal,2-heptanal, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols suchas 1-butanal, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol,geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol,3-methyl-3-buten-1-ol, 1-pentenol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate; esters such asbutyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethylbutyrate, ethyl caproate, ethyl cinnamate, ethyl crotonate, ethylformate, ethyl isobutyrate, ethyl isovalerate, ethylalpha-methylbutyrate, ethyl propionate, ethyl salicylate,trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, hexylbutyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methylbutyrate, methyl caproate, methyl isobutyrate, alpha-methylbutyrate,propyl acetate, amyl acetate, amyl butyrate, benzyl salicylate, dimethylanthranilate, ethyl methylphenylglycidate, ethyl succinate, isobutylcinnamate and terpenyl acetate; essential oils, such as jasmin absolute,rose absolute, orris absolute, lemon essential oil, Bulgarian rose, yarayara, natural raspberry oil and vanilla; lactones; sulfides, e.g.,methyl sulfide and other materials such as maltol, pulegone mercaptan,alpha-phellandrene, ethyl maltol, 2,2,4,4,6,6-hexamethyl-S-trithiane,acetoin and acetals, (e.g., 1,1-diethoxyethane, 1,1-dimethoxyethane anddimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,be capable of providing an environment in which the organolepticallyuseful hydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention can be dispersed or admixed to provide a homogeneous medium.In addition, selection of one or more flavoring adjuvants, as well asthe quantities thereof, will depend upon the precise organolepticcharacter desired in the finished product. Thus, in the case offlavoring compositions, ingredient selection will vary in accordancewith the foodstuff to which the flavor and aroma are to be imparted. Incontradistinction, in the preparation of solid products, e.g., simulatedfoodstuffs, ingredients capable of providing normally solid compositionsshould be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of theorganoleptically useful hydroxyl-and-cyano-substituted sulfur-containingcompounds of our invention employed in a particular instance can varyover a relatively wide range whereby to its desired organoleptic effectshaving reference to the nature of the product are achieved. Thus,correspondingly greater amounts would be necessary in those instanceswherein the ultimate food composition to be flavored is relatively blandto the taste, whereas relatively minor quantities may suffice forpurposes of enhancing the composition merely deficient in natural flavoror aroma. The primary requirement is that the amount selected to beeffective, i.e, sufficient to alter the organoleptic characteristics ofthe parent composition, whether foodstuff per se of flavoringcomposition.

The use of insufficient quantities of the organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention will, of course, substantially vitiate any possibility ofobtaining the desired results while excess quantities prove needlesslycostly and in extreme cases, may disrupt the flavor-aroma balance, thusproving self-defeating. Accordingly, the terminology "effective amount"and "sufficient amount" is to be accorded a significance in the contextof the present invention consistent with the obtention of desiredflavoring effects.

Thus, and with respect to ultimate food compositions, it is found thatquantities of the organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention ranging from a small buteffective amount, e.g., about 0.1 parts per million up to about 50 partsper million by weight based on total composition (more preferably, fromabout 0.2 ppm up to about 10 ppm) are suitable. Concentrations in excessof the maximum quantity stated are not normally recommended since theyfail to prove commensurate with enhancement of organoleptic properties.In those instance wherein the organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention are added to the foodstuff as an integral component of aflavoring composition it is, of course, essential that the totalquantity of flavoring composition employed be sufficient to yield aneffective organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention in concentrations ranging from about 0.1% up to about 15% byweight based on the total weight of said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention with, for example, gum arabic, gum tragacanth, carageenan andthe like, and thereafter spray-drying the resultant mixture whereby toobtain the particular solid product. Pre-prepared flavor mixed in powderform, e.g., a fruit flavored powder mix, is obtained by mixing the driedsolid components, e.g., starch, sugar and the like, and theorganoleptically useful hydroxyl-and-cyano-substituted sulfur-containingcompounds of our invention in a dry blender until the requisite degreeof uniformity is achieved.

It is presently preferred to combine with the organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Vanillin;

Methyl cinnamate;

Ethyl perlargonate;

Methyl anthranilate;

Isoamyl acetate;

Isobutyl acetate;

Alpha-ionone;

Ethyl butyrate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Ethyl acetate;

Anethole;

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine(4-allyl-1,2,6-trimethoxy benzene);

Isoelemecine(4-propenyl-1,2,6-trimethoxybenzene);

2-(4-Hydroxy-4-methylpentyl)norbornadiene prepared according to U.S.patent application Ser. No. 461,703 filed on Apr. 17, 1974, now U.S.Pat. No. 3,886,289;

Natural blackcurrent juice;

Buchu leaf oil;

Alpha-phellandrene;

Cis-3-hexen-1-ol;

Terpinenol-4;

Ethyl maltol;

Methyl benzoate;

Benzaldehyde;

Coriander oil;

Alpha-ionone;

Ethyl heptanoate;

Ethyl anthranilate;

Cinnamic alcohol;

Amyl valerinate;

Cinnamyl propionate;

Rhodinyl acetate;

Methyl beta-hydroxy butyrate;

Ethyl beta-hydroxy butyrate;

2-Phenyl-3-carboethoxyfuran;

Cyclohexyl disulfide;

Grapefruit oil

Nootkatone;

Bergamot oil;

Citral;

Amyl alcohol;

5-Phenyl-4-pentenal;

5-Phenyl-2-pentenal;

Allyl caproate;

2-(n-Pentyl)thiazole;

2-(i-Butyl)thiazole;

2-(i-Propyl)thiazole;

2-(n-propyl)thiazole;

2-Phenyl-4-pentenal;

2-Phenyl-4-pentenaldimethylacetal;

Methional;

4-Methylthiobutanal;

2-Ethyl-3-acetylpyrazine;

Tetramethyl pyrazine;

2-Methyl pyrazine;

Trans-2-hexenal;

Hydrolyzed vegetable protein;

Monosodium glutamate;

Dimethyl disulfide;

Methyl propyl disulfide;

Methyl propenyl disulfide;

Methyl allyl disulfide;

Allyl propyl disulfide;

Propyl propenyl disulfide;

Dipropyl disulfide;

Diallyl disulfide;

Propyl propenyl trisulfide;

Thiopropanal-S-oxide;

Thiobutanal-S-oxide;

Thioethanal-S-oxide;

Thiohexanal-S-oxide; and

Propyl propene thiosulfonate.

The following Examples I(A), I(B) and II are given to illustrate methodsof preparing the organoleptically useful hydroxyl-and-cyano-substitutedsulfur-containing compounds of our invention. The examples followingExample II set forth methods whereby the organoleptically usefulhydroxyl-and-cyano-substituted sulfur-containing compounds of ourinvention are utilized for their organoleptic properties.

It will be understood that these examples are illustrative and theinvention is not to be considered as restricted thereto except asindicated in the appended claims.

EXAMPLE I(A) preparation of cyano-substituted sulfur-containingcompounds

Reactions: ##STR73##

Into a 1 liter reaction vessel equipped with thermometer, stirrer,condenser and heating mantle is placed 455.0 grams (3.0 moles) ofgeranonitrile, a mixture of compounds having the structures: ##STR74##The geranonitrile is heated with stirring to 65° C. Dropwise, over aperiod of 60 minutes, while maintaining the reaction temperature at 65°C., 190.0 grams (2.5 moles) of thioacetic acid is added to the reactionmass.

The reaction mass is then stirred at 65°-70° C. of one hour. Thereaction mass is then heated and maintained at 70°-75° C. for a periodof 1.25 hours causing the reaction: ##STR75## to take place.

The reaction mass is then cooled and 200 cc toluene is added thereto.The organic layer is separated from the aqueous phase and the organiclayer is washed with one 200 cc portion of 20% aqueous sodium hydroxidecausing the reactions: ##STR76## PG,79 to take place.

The resulting washed product is then distilled on a 6" stone packedcolumn yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         90/100  120/125   3.0/3.0                                                                              15.0                                       2         100     135       3.5    15.0                                       3         105     145       3.5    40.0                                       4         105     160       3.5    50.0                                       5         108     175       3.5    60.0                                       6         108     177       3.0    30.0                                       7         108     179       3.0    45.0                                       8         108     181       3.0    20.0                                       ______________________________________                                    

whereby the reaction: ##STR77## takes place.

The resulting distillation product is then bulked and redistilled on aspinning band column yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         90/95   110/141   2.5/2.5                                                                              10.0                                       2          95     150       2.5    30.0                                       3          95     150       2.5     5.0                                       4         108     158       2.5    30.0                                       5         108     165       2.5    24.0                                       6         108     165       2.5    29.0                                       7         108     170       2.5    27.0                                       8         108     195       2.8     36.0.                                     ______________________________________                                    

FIG. 1 is the GLC profile for the crude reaction product. The peakindicated by reference numeral 10 is the peak for the compound havingthe structure: ##STR78##

FIG. 2 is the GLC profile for fraction 6 of the second distillation(Conditions: SE-30 column programmed at 100°-220° C. at 8° C. perminute). The peak indicated by reference numeral 20 is the peak for thecompound having the structure: ##STR79##

FIG. 3 is the NMR spectrum for the compound having the structure:##STR80##

FIG. 4 is IR spectrum for the compound having the structure: ##STR81##

The compound having the structure: ##STR82## has a natural natural buchuleaf, tomato leaf, herbaceous, basil, minty and grapefruit-like aromawith natural "ontiga", tomato leaf, minty and grapefruit-like undertonesfrom a fragrance standpoint.

From a flavor standpoint the compound having the structure: ##STR83##has a green, minty, grapefruit-like and nootkatone-like aroma and tasteprofile.

The compounds having the structures: ##STR84## each has a natural buchuleaf, tomato leaf, herbaceous, basil, minty and grapefruit-like aromawith natural "ontiga", tomato leaf, minty anbd grapefruit-likeundertones from a fragrance standpoint, twofold the intensity andsubstantivity of the compound having the structure: ##STR85##

From a flavor standpoint each of the compounds having the structures:##STR86## each has a green, minty, grapefruit-like and nootkatone-likearoma and taste profile twofold the intensity of the compound having thestructure: ##STR87##

EXAMPLE I(B) Prepartaion of Cyano-Substituted Sulfur-ContainingCompounds

Reactions: ##STR88##

Into a 1 liter reaction vessel equipped with thermometer, stirrer,condenser and heating mantle is placed 455.0 grams (3.0 moles) ofgeranonitrile, the compound having the structure: ##STR89##

The geranonitrile is heated with stirring to 65° C. Dropwise, over aperiod of 60 minutes, while maintaining the reaction temperature at 65°C., 190.0 grams (2.5 moles) of thioacetic acid is added to the reactionmass.

The reaction mass is then stirred at 65°-70° C. for one hour. Thereaction mass is then heated and maintained at 70°-75° C. for a periodof 1.25 hours causing the reaction: ##STR90## to take place.

The reaction mass is then cooled and 200 cc toluene is added thereto.The organic layer is separated from the aqueous phase and the organiclayer is washed with one 200 cc portion of 20% aqueous sodiumbicarbonate causing the reactions: ##STR91## to take place. Theresulting washed product is then distilled on a 6" stone packed columnyielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         90/100  120/125   3.0/3.0                                                                              15.0                                       2         100     135       3.5    15.0                                       3         105     145       3.5    40.0                                       4         105     160       3.5    50.0                                       5         108     175       3.5    60.0                                       6         108     177       3.0    30.0                                       7         108     179       3.0    45.0                                       8         108     181       3.0    20.0                                       ______________________________________                                    

whereby the reaction: ##STR92## takes place.

The resulting distillation product is then bulked and redistilled as aspinning band column yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         90/95   110/141   2.5/2.5                                                                              10.0                                       2          95     150       2.5    30.0                                       3          95     150       2.5     5.0                                       4         108     158       2.5    30.0                                       5         108     165       2.5    24.0                                       6         108     165       2.5    29.0                                       7         108     170       2.5    27.0                                       8         108     195       2.8     36.0.                                     ______________________________________                                    

FIG. 5 is the GLC profile for the sodium bicarbonate washed crudeproduct. The peaks indicated by reference numeral 150 are the peaks forthe compounds having the structures: ##STR93## The peak indicated byreference numeral 152 is the peak for the compound having the structure:##STR94## The peaks indicated by reference numeral 153 are the peaks forthe compounds having the structures: ##STR95## The peak indicated byreference numeral 154 is the peak for the compound having the structure:##STR96##

FIG. 6 is the GLC profile for the water washed crude reaction product.

The peaks indicated by reference numeral 160 are the peaks for thecompounds having the structures: ##STR97##

The peak indicated by reference numeral 162 is the peak for the compoundhaving the structure: ##STR98##

The peaks indicated by reference numeral 163 are the peaks for thecompound having the structures: ##STR99##

The compounds having the structures: ##STR100## each has a natural buchuleaf, tomato leaf, herbaceous, basil, minty and grapefruit-like aromawith natural "ontiga", tomato leaf, minty and grapefruit-like undertonesfrom a fragrance standpoint, with an intensity twofold that of thecompound having the structure: ##STR101## and a substantially twofoldthat of the compound having the structure: ##STR102##

From a flavor standpoint the compounds having the structures: ##STR103##each has a green, minty, grapefruit-like and nootkatone-like aroma andtaste profile approximately twice the intensity of the compound havingthe structure: ##STR104##

EXAMPLE II Preparation of S(4-Hydroxy-1-Isopropyl-4-Methylhexyl)Thioacetate

Reaction: ##STR105##

Into a 1 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle is placed 468.0 grams (3.0 moles) ofdihydrollinalool having the structure: ##STR106## The dihydrolinalool isheated to 65° C. with stirring. While maintaining the dihydrolinalool at65° C., dropwise over a period of one hour, thioacetic acid having thestructure: ##STR107## is added to the reaction mass. After addition ofthe thioacetic acid, the reaction mass is maintained at 65°-70° C. for aperiod of one hour. The reaction mass is then heated to 85°-90° C. for aperiod of one hour with stirring.

The reaction mass is then cooled and washed with two 200 cc portions of20% aqueous sodium hydroxide.

The resulting product is distilled on a 4" splash column yielding thefollowing fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         75/92   80/90     3.8/3.8                                                                              200.0                                      2          98     105       3.5    200.0                                      3         125     145       3.5     41.0                                      4         150     200       3.5     280.0.                                    ______________________________________                                    

The resulting product has the structure: ##STR108##

FIG. 5 is the GLC profile for the crude reaction product (Conditions:SE-30 column programmed at 100°-220° C. at 8° C. per minute). The peakindicated by reference numeral 50 is the peak for the compound havingthe structure: ##STR109##

FIG. 6 is the GLC profile for fraction 4 of the distillation product ofthe reaction product of this example. The peak indicated by referencenumeral 60 is the peak for the compound having the structure: ##STR110##

FIG. 7 is the NMR spectrum for the compound having the structure:##STR111##

FIG. 8 is the infra-red spectrum for the compound having the structure:##STR112##

EXAMPLE III(A) IMPREGNATED PLASTICS AND AIR FRESHENERS

Scented polyethylene pellets having pronounced natural buchu leaf,tomato leaf, herbaceous, basil, minty and grapefruit-like aromas withnatural "ontiga" tomato leaf, minty and grapefruit-like undertones areprepared as follows:

75 Pounds of polyethylene having a melting point of about 220° F. isheated to about 230° F. in a container of the kind illustrated in FIGS.11 and 12. 12.5 Pounds of tetrahydro-5-isopropyl-2-methyl-2-thiopheneacetonitrile having the structure: ##STR113## prepared according toExample I, supra, are then quickly added to the liquified polyethylene.The lid 228 is put in place and the agitating means 273 are actuated.The temperature is maintained at about 225° F. and the mixing iscontinued for about 15 minutes. The valve "V" is then opened to allowflow of the molten polyethylene enriched with thetetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile containingmaterial through the orifices 234 (whereby such material exits throughorifices 234). The liquid falling through the orifices 234 solidifiesalmost instantaneously upon impact with the moving cooled conveyor 238.Polyethylene beads or pellets 224 having a pronounced aroma as set forthabove are thus formed. These pellets may be called "master pellets".

50 Pounds of the aroma-containing "master pellets" are then added to1000 pounds of unscented and untreated polyethylene powder and the massis heated to the liquid state. The liquid is molded into thin sheets orfilms. The thin sheets or films have pronounced aromas as set forth,supra. The sheets or films are cut into strips 1/4" in width x 3" inlength and employed in standard air freshening apparatus.

On operation of the standard air freshening apparatus is a room airfreshener, after 4 minutes, the room has an aesthetically pleasing aromaas set forth, supra.

EXAMPLE II(B) TREATED PLASTICS AND AIR FRESHENER

100 Pounds of polypropylene are heated to about 300° F. 15 Pounds oftetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile preparedaccording to Example I are added to the liquified polypropylene. Theprocedure is carried out in the apparatus shown in FIGS. 11 and 12.After mixing for about 8 minutes, the valve "V" is opened to allow theexit of polypropylene mixture which has been treated with thetetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile whereby solidpellets having pronounced aromas described as "natural buchu leaf,tomato leaf, herbaceous, basil, minty and grapefruit-like with natural"ontiga", tomato leaf, minty and grapefruit-like undertones"are formedon the conveyor. The pellets thus obtained are then admixed with about20 times their weight of unscented polypropylene and untreatedpolypropylene and the mixture is heated and molded into "spaghetti"tows. The "spaghetti" tows are cut into small cylinders approximately0.1 inches in length x 0.2 inches in diameter. The cylinders have strongand pleasant aromas as described, supra.

The cylinders are used in standard air freshening apparatus to produceaesthetically pleasing aromas as set forth, supra, with no foul odors inenvironments surrounding the air freshener apparatus.

A portion of the cylinders are ground into small particles to be used inthe deodorant stick of Example III(C).

EXAMPLE III(C) DEODORANT STICK

A deodorant stick composition is prepared containing the followingmaterials:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Propylene Glycol    65.00                                                     Sodium stearate     7.00                                                      Distilled water     23.75                                                     IRGSAN ® DP-300 0.25                                                      (2,4,4-trichloro-2'-hydroxy                                                   diphenyl ether, manufactured                                                  by the Ciba Geigy Chemical                                                    Company and the trademark of                                                  the Ciba Geigy Chemical Company                                               of Hastings on Hudson, New York)                                              Ground polymer containing                                                                         4.00                                                      tetrahydro-5-isopropyl-2-                                                     methyl-2-thiopene aceto-                                                      nitrile produced according                                                    to Example III(B), supra.                                                     ______________________________________                                    

The ingredients are combined without the ground polymer and are heatedto 75° C. These ingredients are mixed and continued to be heated untilthe sodium stearate has dissolved. The resulting mixture is cooled to40° C. and the ground fragrance-containing polymer is added and mixed at40° C. until a suspension is formed. The resulting suspension is cooledand formed into sticks and the deodorant sticks exhibit a pleasant freshgreen aroma when utilized in the axillary areas of a human being.

EXAMPLE III(D) IMPREGNATED PLASTICS AND AIR FRESHENERS

Scented polyethylene pellets having a pronounced green, floral and rosearoma are prepared as follows:

75 pounds of polyethylene having a melting point of about 220° F. isheated to about 230° F. in a container of the kind illustrated in FIGS.11 and 12. 12.5 Pounds of one or a mixture of mercaptans having thestructures: ##STR114## prepared according to Example I are then quicklyadded to the liquified poly- ethylene. The lid 228 is put in place andthe agitating means 273 are actuated. The temperature is maintained atabout 225° F. and the mixing is continued for about 15 minutes. Thevalve "V" is then opened to allow flow of the molten polyethyleneenriched with the mercaptan-containing material through the orifices 234whereby such material exits through orifices 234. The liquid fallingthrough the orifices 234 solidifies almost instantaneously upon impactwith the moving cooled conveyor 238. Polyethylene beads or pellets 224having a pronounced aroma as set forth above are thus formed. Thesepellets may be called "master pellets".

50 Pounds of the aroma-containing "master pellets" are then added to1000 pounds of unscented and untreated polyethylene powder and the massis heated to the liquid state. The liquid is molded into thin sheets orfilms. The thin sheets or films have pronounced aromas as set forth,supra. The sheets or films are cut into strips 1/4" in width x 3" inlength and employed in standard air freshening apparatus.

On operation of the standard air freshening apparatus as a room airfreshener, after 4 minutes, the room has an aesthetically pleasing aromaas set forth, supra.

EXAMPLE III(E) DEODORANT STICK

A deodorant stick composition is prepared containing the followingmaterials:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Propylene Glycol      65.00                                                   Sodium stearate       7.00                                                    Distilled water       23.75                                                   IRGSAN ® DP-300   0.25                                                    (2,4,4-trichloro-2'-hydroxy                                                   diphenyl ether, manufactured                                                  by the Ciba Geigy Chemical                                                    Company and the trademark of                                                  the Ciba Geigy Chemical Company                                               of Hastings on Hudson, New York)                                              Ground polymer containing                                                                           4.00                                                    one or a mixture of the                                                       mercaptans having the structures:                                              ##STR115##                                                                    ##STR116##                                                                    ##STR117##                                                                   and                                                                            ##STR118##                                                                   prepared according                                                            to Example III(D), supra.                                                     ______________________________________                                    

The ingredients are combined without the ground polymer and are heatedto 75° C. These ingredients are mixed and continued to be heated untilthe sodium stearate has dissolved. The resulting mixture is cooled to40° C. and the ground fragrance-containing polymer is added and mixed at40° C. until a suspension is formed. The resulting suspension is cooledand formed into sticks and the deodorant sticks exhibit a pleasant freshgreen aroma when utilized in the axillary areas of a human being.

EXAMPLE IV GRAPEFRUIT FLAVOR FORMULATION

Thc following formulation is prepared:

    ______________________________________                                                        Parts by Weight                                                               EXAMPLE                                                       Ingredients       IV(A)    IV(B)    IV(C)                                     ______________________________________                                        Grapefruit oil    92.0     92.0     92.0                                      Bergamot oil      2.0      2.0      2.0                                       Citral            3.0      3.0      3.0                                       n-Amyl alcohol    1.0      1.0      1.0                                       Ethyl acetate     1.0      1.0      1.0                                       2-Methyl-4-phenyl-1-                                                                            1.5      0.0      0.0                                       pentanol produced                                                             according to U.S.                                                             Pat. No. 4,632,831                                                            2-Methyl-4-phenyl-1-                                                                            0.0      1.8      0.0                                       pentanol acetate                                                              produced according to                                                         U.S. Pat. No. 4,632,831                                                       Tetrahydro-5-isopropyl-2-                                                                       2.0      2.0      0.0                                       methyl-2-thiophene acetonitrile                                               produced according to                                                         Example I, supra                                                              One of the mercaptans having                                                                    0.0      0.0      1.0                                       one of the structures:                                                         ##STR119##                                                                    ##STR120##                                                                    ##STR121##                                                                   and                                                                            ##STR122##                                                                   prepared according                                                            to Example I, supra.                                                          ______________________________________                                    

When the above grapefruit formulations are added to water at the rate of1%, an excellent grapefruit drink is prepared. Thetetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile as well as eachof the mercaptans having the structures: ##STR123## of our inventiongives a minty, natural green nuance to the above two formulationsthereby rendering them more "natural-like". Furthermore, the formulationare both "nootkatone" like with aesthetically pleasing red grapefruitnotes.

When the above formulations are modified by adding to them 1.5 parts byweight of any of the following ingredients a yet more natural grapefruitpeel aroma and taste is imparted thereto:

(1,3-diethylacetonyl)(1,3-diisopropylacetonyl)sulfide;

3-methyl-thio-4-heptanone;

3-propyl-thio-4-heptanone;

3-(methallylthio)-2,6-dimethyl-4-heptanone;

3-crotylthio-2,6-dimethyl-4-heptanone; and

3-allylthio-2,6-dimethyl-4-heptanone.

EXAMPLE V

(I) The following concentrates are prepared:

    ______________________________________                                                             Parts by Weight                                          Ingredients            V(A)    V(B)                                           ______________________________________                                        Geraniol               1.00    1.00                                           Ethyl methyl phenyl glycidate                                                                        3.50    3.50                                           Nootkatone             5.00    5.00                                           Ethyl pelargonate      5.00    5.00                                           Isoamyl acetate        4.00    4.00                                           Vanillin               2.00    2.00                                           Isobutyl-2-methyl-pentenoate                                                                         3.00    3.00                                           2-Methyl-4-phenyl-1-pentanol acetate                                                                 1.00    1.00                                           2-Methyl-4-phenyl-1-pentanol                                                                         1.13    1.13                                           Tetrahydro-5-isopropyl-2-                                                                            1.00    0.00                                           methyl-2-thiophene                                                            acetonitrile                                                                  One of the mercaptan   0.00    0.50                                           having the structures:                                                         ##STR124##                                                                    ##STR125##                                                                    ##STR126##                                                                   and                                                                            ##STR127##                                                                   ______________________________________                                    

(II) One volume of one of the concentrates prepared in Part (I), supra,is dissolved in four volumes of propylene glycol and the mixture isadded to a hard candy melt at the rate of 1.5 ounces of the concentratesolution per 100 pounds of melt. After the finished candy has beenproduced, it is found to have an excellent grapefruit flavor. When thecandy is compared with candy made under the same conditions but withoutthe tetra-5-isopropyl-2-methyl-2-thiophene acetonitrile or one of themercaptans having the structures: ##STR128## of our invention, it isfound to have an inferior grapefruit flavor. Indeed, the grapefruitflavor used with the tetrahydro-5-isopropyl-2-methyl-2-thiopheneacetonitrile or one of the mercaptans having the structures: ##STR129##of our invention is markedly superior than without thetetrahydro-5-isopropyl-2- methyl-2-thiophene acetonitrile or mercaptansof our invention.

EXAMPLE VI A. Powder Flavor Formulation

Twenty grams of one of the flavor formulations of Example IV isemulsified in a solution containing 300 grams gum acacia and 700 gramsof water. The emulsion is spray-dried with a Bowen Lab Model Drierutilizing 260 c.f.m. of air with an inlet temperature of 500° F., anoutlet temperature of 200° F. and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        One of the Liquid     20                                                      grapefruit flavors                                                            of Example IV                                                                 Propylene glycol      9                                                       CAB-O-SIL ® M-5   5                                                       (Brand of silica produced by                                                  the Cabot Corporation of                                                      125 High Street, Boston,                                                      Mass. 02110);                                                                 Physical Properties:                                                          Surface area:  200m.sub.2 /gram                                               Nominal particle size:                                                                       0.012 microns                                                  Density:       2.3 lbs./cu. ft.                                               ______________________________________                                    

The CAB-O-SIL® is dispersed in one of the liquid grapefruit flavorcompositions of Example IV with vigorous stirring thereby resulting in aviscous liquid. 71 Parts by weight of the powder flavor composition ofPart "A", supra, is then blended into said viscous liquid with stirringat 25° C. for a period of thirty minutes resulting in a dry,free-flowing, sustained release grapefruit flavored powder.

EXAMPLE VII

Ten parts by weight of 50 Bloom pigskin gelatin is added to ninety partsby weight of water at a temperature of 150° C. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. Twenty parts by weight of one of the liquid grapefruit flavorcompositions of Example IV is added to the solution which is thenhomogenized to form an emulsion having a particle size typically in therange of 5-40 microns. The material is kept at 120° F. under whichconditions the gelatin will not jell.

Coacervation is induced by adding slowly and uniformly forty parts byweight of a 20% aqueous solution of sodium sulfate. During coacervation,the gelatin molecules are deposited uniformly about each oil droplet asa nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000parts by weight of 7% aqueous solution of sodium sulfate at 65° F. Theresulting jelled coacervate may be filtered and washed with water attemperatures below the melting point of gelatin to remove the salt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE VIII Chewing Gum

One hundred parts by weight of chicle are mixed with four parts byweight of one of the flavors prepared in accordance with Example VI(B).Three hundred parts of sucrose and one hundred parts of corn syrup areadded. Mixing is effected in a ribbon blender with jacketed walls of thetype manufactured by the Baker Perkins Company.

The resultant chewing gum blend is then manufactured into strips oneinch in width and 0.1 inches in thickness. The strips are cut intolengths of three inches each. On chewing, the chewing gum has a pleasantlong-lasting grapefruit flavor.

EXAMPLE IX Chewing Gum

One hundred parts by weight of chicle are mixed with eighteen parts byweight of one of the flavors prepared in accordance with Example VII.Three hundred parts of sucrose and one hundred parts of corn syrup arethen added. Mixing is effected in a ribbon blender with jacketed wallsof the type manufactured by the Baker Perkins Company.

The resultant chewing gum blend is then manufactured into strips oneinch in width and 0.1 inches in thickness. The strips are cut intolengths of three inches each. On chewing, the chewing gum has apleasant, long-lasting grapefruit flavor.

EXAMPLE X Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight                                                                              Ingredient                                                     ______________________________________                                        Group "A"                                                                     30.200         Glycerine                                                      15.325         Distilled water                                                .100           Sodium benzoate                                                .125           Saccharin sodium                                               .400           Stannous flurode                                               Group "B"                                                                     12.500         Calcium carbonate                                              37.200         Dicalcium phosphate dihydrate                                  Group "C"                                                                     2.000          Sodium n-lauroyl sarcosinate                                                  (foaming agent)                                                Group "D"                                                                     1.200          One of the flavor materials                                                   of Example VI(B).                                              ______________________________________                                    

Procedure:

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly, the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenizedand finally tubed.

The resulting toothpaste, when used in a normal tooth brushingprocedure, yields a pleasant grapefruit flavor of constant strongintensity throughout said procedure (1-1.5 minutes).

EXAMPLE X Chewable Vitamin Tablets

One of the flavor materials produced according to the process of ExampleVII is added to a chewable vitamin tablet formulation at the rate of tengrams per kilogram which chewable vitamin tablet formulation is preparedas follows:

In a Hobart mixer, the following materials are blended to homogeneity:

    ______________________________________                                                              Grams/1000                                              Ingredients           Tablets                                                 ______________________________________                                        Vitamin C (ascorbic acid)                                                                           70.110                                                  as ascorbic acid-sodium                                                       ascorbate mixture 1:1                                                         Vitamin B.sub.1 (thiamine mononitrate                                                               4.000                                                   as ROCOAT ® thiamine mononitrate                                          331/3% (Hoffman LaRoche)                                                      Vitamin B.sub.2 (riboflavin) as                                                                     5.000                                                   ROCOAT ® riboflavin 331/3%                                                Vitamin B.sub.6 (pyridoxine hydro-                                                                  4.000                                                   chloride) as ROCOAT ® phridoxine                                          hydrochloride 331/3%                                                          Niacinamide as ROCOAT ®                                                                         33.000                                                  niacinamide 331/3%                                                            Calcium pantothenate  11.500                                                  Vitamin B.sub.12 (cyanocobalamin) as                                                                3.500                                                   Merck 0.1% in gelatin                                                         Vitamin E (dl-alpha tocopheryl                                                                      6.600                                                   acetate) as dry Vitamin E acetate                                             331/3%                                                                        d-Biotin              0.044                                                   One of the flavor materials of                                                                      (as indicated                                           Example VII           above)                                                  Certified lake color  5.000                                                   Sweetener, sodium saccharin                                                                         1.000                                                   Magnesium stearate lubricant                                                                        10.000                                                  Mannitol q.s. to make 500.000                                                 ______________________________________                                    

Preliminary tablets are prepared by slugging with flat faced punches andgrinding the slugs to 14 mesh. 13.5 Grams dry Vitamin A acetate and 0.6grams Vitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 grams each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong grapefruit flavor for a period of a 12 minutes.

EXAMPLE XII Herbal Perfume Formulation

The following mixtures are prepared:

    ______________________________________                                                         Parts by Weight                                                               EXAMPLES                                                     Ingredients        XI(A)    XI(B)   XI(C)                                     ______________________________________                                        Oakmoss absolute (50% in                                                                         20       20      20                                        diethyl phthalate)                                                            Alpha-methyl-3,4,methylene-                                                                      10       10      10                                        dioxyhydrocinnamic                                                            aldehyde                                                                      Methyl dihydrojasmonate                                                                          100      100     100                                       Coumarin           20       20      20                                        Musk ketone        80       80      80                                        Isocyclocitral (10% in                                                                           10       10      10                                        diethyl phthalate)                                                            Galbanum oil (10% in diethyl                                                                      6        6       6                                        phthalate)                                                                    Rosemary oil       10       10      10                                        Pine needle oil    60       60      60                                        Fir balsam absolute (10% in                                                                      10       10      10                                        diethyl phthalate)                                                            Bergamot oil       60       60      60                                        Lemon oil          14       14      14                                        Benzyl acetate     468      468     468                                       Linalool           80       80      80                                        Indole (10% in diethyl phthalate)                                                                 6        6       6                                        Undecalactone (10% in diethyl                                                                    12       12      12                                        phthalate)                                                                    2-methyl-4-phenyl-1-pentanol                                                                     12        0       0                                        (produced according to                                                        U.S. Letters Patent                                                           No. 4,632,831)                                                                2-methyl-4-phenyl-1-pentanol                                                                     `0       20       5                                        acetate (produced according to                                                U.S. Letters Patent                                                           No. 4,632,831)                                                                Tetrahydro-5-isopropyl-2-                                                                        10        5       0                                        methyl-2-thiophene acetonitrile                                               produced according to                                                         Example I, supra.                                                             One of the mercaptans                                                         having the structures:                                                         ##STR130##                                                                    ##STR131##                                                                    ##STR132##                                                                   and                 0        0       5                                         ##STR133##                                                                   prepared according                                                            to Example I, supra.                                                          ______________________________________                                    

The addition to this herbal formulation of the tetra-5isopropyl-2-methyl-2-thiophene acetonitrile or one of the mercaptanshaving one of the structures: ##STR134## imparts to this herbalformulation as excellent natural buchu leaf, tomato leaf, herbaceous,basil, minty and grapefruit-like topnotes, with natural "ontiga", tomatoleaf, minty and grapefruit-like undertones. Accordingly, theformulations can be described as "herbaceous with natural buchu leaf,tomato leaf, herbaceous, basil, minty and grapefruit-like topnotes andnatural "ontiga", tomato leaf, minty and grapefruit-like undertones".

EXAMPLE XIII Preparation of Cosmetic Powder Compositions

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table II below. Each of the cosmetic powder Compositions has anexcellent aroma as described in Table II below.

                  TABLE II                                                        ______________________________________                                        Substance        Aroma Description                                            ______________________________________                                        Tetrahydro-5-isopropyl-2-                                                                      A natural buchu leaf,                                        methyl-2-thiophene aceto-                                                                      tomato leaf, herbaceous,                                     nitrile produced according                                                                     basil, minty and grapefruit-                                 to Example I.    like aroma profile with                                                       natural "ontiga", tomato                                                      leaf, minty and grape-                                                        fruit-like undertones.                                        ##STR135##                                                                                     ##STR136##                                                   ##STR137##      A natural buchu leaf, tomato leaf, herbaceous, basil,                         minty and grapefruit-like aroma profile with natural                          "ontiga", tomato leaf, minty and grapefruit-like                              undertones,                                                   ##STR138##      A natural buchu leaf, tomato leaf, herbaceous, basil,                         minty and grapefruit-like aroma profile with natural                          "ontiga", tomato leaf, minty and grapefruit-like                              undertones,                                                   ##STR139##      A natural buchu leaf, tomato leaf, herbaceous, basil,                         minty and grapefruit-like aroma profile with natural                          "ontiga", tomato leaf, minty and grapefruit-like                              undertones,                                                  Perfume formulations                                                                           A herbaceous aroma with                                      of Example XII.  natural buchu leaf, tomato                                                    leaf, herbaceous, basil, minty                                                and grapefruit-lile topnotes                                                  and natural "ontiga", tomato                                                  leaf, minty and grape-                                                        fruit-like undertones.                                       ______________________________________                                    

EXAMPLE XVI Perfumed Liquid Detergents

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issuedApr. 6, 1976 incorporated by reference herein) with aroma nuances as setforth in Table II of Example XIII are prepared containing 0.10%, 0.15%,0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in Table II ofExample XIII. They are prepared by adding and homogeneously mixing theappropriate quantity of substance set forth in Table II of Example XIIIin the liquid detergent. The detergents all possess excellent aromas asset forth in Table II of Example XIII, the intensity increasing withgreater concentrations of substance as set forth in Table II of ExampleXIII.

EXAMPLE XV Preparation OF Colognes and Handkerchief Perfumes

Compositions as set forth in Table II of Example XIII are incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% in80%, 85%, 90% and 95% aqueous food grade ethanol solutions; and intohandkerchief perfumes at concentrations of 15%, 20%, 25% and 30% (in80%, 85%, 90% and 95% aqueous food grade ethanol solutions). Distinctiveand definite fragrances as set forth in Table II of Example XIII areimparted to the colognes and to the handkerchief perfumes at all levelsindicated.

EXAMPLE XVI Preparation of Soap Compositions

One hundred grams of soap chips (per sample)(IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table II of Example XIIIuntil homogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under eight atmospheres pressure at180° C. for a period to three hours and the resulting liquids are placedinto soap molds. The resulting soap cakes, on cooling, manifest aromasas set forth in Table II of Example XIII.

EXAMPLE XVII Preparation of Solid Detergent Compositions

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948 (incorporated by referenceherein):

    ______________________________________                                        Ingredient           Percent by Weight                                        ______________________________________                                        "NEODOL ® 45-11 (a C.sub.14 --C.sub.15                                                         12                                                       alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate     55                                                       Sodium citrate       20                                                       Sodium sulfate, water                                                                              q.s.                                                     brighteners                                                                   ______________________________________                                    

This detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table II of Example XIII. Each ofthe detergent samples has an excellent aroma as indicated in Table II ofExample XIII.

EXAMPLE XVIII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated herein by reference),nonwoven cloth substrates useful as drier-added fabric softeningarticles of manufacture are prepared wherein the substrate, thesubstrate coating, the outer coating and the perfuming material are asfollows:

1. A water "dissolvable" paper ("Dissolvo Paper"); and

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and pH3 Anouter coating having the following formulation (m.p. about 150° F.):

    ______________________________________                                        57%         C.sub.20--22 HAPS                                                 22%         isopropyl alcohol                                                 20%         antistatic agent                                                   1%         of one of the substances as set forth in                                      Table II of Example XIII.                                         ______________________________________                                    

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table II of Example XIII, supra, consist of a substrate coatinghaving a weight of about 3 grams per 100 square inches of substrate; afirst coating located directly on the substrate coating consisting ofabout 1.85 grams per 100 square inches of substrate; and an outercoating coated on the first coating consisting of about 1.4 grams per100 square inches of substrate. One of the substances of Table II ofExample XIII is admixed in each case with the outer coating mixture,thereby providing a total aromatized outer coating weight ratio tosubstrate of about 0.5:1 by weight of the substrate. The aromacharacteristics are imparted in a pleasant manner to the head space in adryer on operation thereof in each case using said drier-added fabricsoftener non-woven fabrics and these aroma characteristics are describedin Table II of Example XIII, supra.

EXAMPLE XIX Hair Spray Formulations

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 West51st Street, New York, N.Y., in 91.62 grams of 95% food grade ethanol.8.0 Grams of the polymer is dissolved in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                                          Weight Percent                                              ______________________________________                                        Dioctyl sebacate    0.05                                                      Benzyl alcohol      0.10                                                      Dow Corning 473 fluid                                                                             0.10                                                      (prepared by the Dow Corning                                                  Corporation)                                                                  TWEEN ® 20 surfactant                                                                         0.03                                                      (prepared by ICI America                                                      Corporation)                                                                  One of the perfumery substances                                                                   0.10                                                      as set forth in Table II of                                                   Example XIII, supra                                                           ______________________________________                                    

The perfuming substances as set forth in Table II of Example XIII addaroma characteristics as set forth in Table II of Example XIII which arerather intense and aesthetically pleasing to the users of the soft-feel,good-hold pump hair sprays.

EXAMPLE XX Conditioning Shampoos

Monamid CMA (prepared by the Mona Industries Company) (3.0 weightpercent) is melted with 2.0 weight percentcoconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol disterate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation)(1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.). This material is "COMPOSITION A".

GAAFQUAT® 755N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, New York)(5.0 weight percent) is admixed with 0.1weight percent sodium sulfite and 1.4 percent polyethylene glycol 6000distearate produced by Armak Corporation. This material is "COMPOSITIONB".

The resulting "COMPOSITION A" and "COMPOSITION B" are then mixed in a50:50 weight ratio of A:B and cooled to 45° C. and 0.3 weight percent ofperfuming substance as set forth in Table II of Example XIII is added tothe mixture. The resulting mixture is cooled to 40° C. and blending iscarried out for an additional one hour in each case. At the end of thisblending period, the resulting material has a pleasant fragrance asindicated in Table II of Example XIII.

EXAMPLE XXI(A) Impregnated Plastics and Air Fresheners

Scented polyethylene pellets having a pronounced green, floral and rosearoma are prepared as follows: 75 Pounds of polyethylene having amelting point of about 220° F. is heated to about 230° F. in a containerof the kind illustrated in FIGS. 11 and 12. 12.5 Pounds ofS(4-hydroxy-1-isopropyl-4-methylhexyl) thioacetate prepared according toExample II are then quickly added to the liquified polyethylene. The lid228 is put in place and the agitating means 273 are actuated. Thetemperature is maintained at about 225° F. and the mixing is continuedfor about 15 minutes. The valve "V" is then opened to allow flow of themolten polyethylene enriched with theS(4-hydroxy-1-isopropyl-4-methylhexyl) thioacetate-containing materialthrough the orifices 234 whereby such material exits through orifices234. The liquid falling through the orifices 234 solidifies almostinstantaneously upon impact with the moving cooled conveyor 238.Polyethylene beads or pellets 224 having a pronounced aroma as set forthabove are thus formed. These pellets may be called "master pellets".

50 Pounds of the aroma-containing "master pellets" are then added to1000 pounds of unscented and untreated polyethylene powder and the massis heated to the liquid state. The liquid is molded into thin sheets orfilms. The thin sheets or films have pronounced aromas as set forth,supra. The sheets or films are cut into strips 1/4" in width×3" inlength and employed in standard air freshening apparatus.

On operation of the standard air freshening apparatus as a room airfreshener, after 4 minutes, the room has an aesthetically pleasing aromaas set forth, supra.

EXAMPLE XXI(B) Treated Plastics and Air Freshener

100 Pounds of polypropylene are heated to about 300° F. 15 Pounds ofS(4-hydroxy-1-isopropyl-4-methylhexyl) thioacetate prepared according toExample II are added to the liquified polypropylene. The procedure iscarried out in the apparatus shown in FIGS. 11 and 12. After mixing forabout 8 minutes, the valve "V" is opened to allow the exit ofpolypropylene mixture which has been treated with theS(4-hydroxy-1-isopropyl-4-methylhexyl) thioacetate, whereby solidpellets having pronounced aromas described as green, floral and rose areformed on the conveyor. The pellets thus obtained are then admixed withabout 20 times their weight of unscented polypropylene ad untreatedpolypropylene and the mixture is heated and molded into "spaghetti"tows. The "spaghetti" tows are cut into small cylinders approximately0.1 inches in length×0.2 inches in diameter. The cylinders have strongand pleasant aromas as described, supra.

The cylinders are used in standard air freshening apparatus to produceaesthetically pleasing aromas as set forth, supra with no foul odors inenvirnonments surrounding the air freshener apparatus.

A portion of the cylinders are ground into small particles to be used inthe deodorant stick of Example XXI(C), infra.

EXAMPLE XXI(C) Deodorant Stick

A deodorant stick composition is prepared containing the followingmaterials:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Propylene Glycol    65.00                                                     Sodium stearate     7.00                                                      Distilled water     23.75                                                     IRGSAN ® DP-300 0.25                                                      (2,4,4-trichloro-2'-hydroxy                                                   diphenyl ether, manufactured                                                  by the Ciba Geigy Chemical                                                    Company of Hastings On Hudson,                                                New York)                                                                     Ground polymer containing                                                                         4.00                                                      fragrance produced according                                                  to Example XXI(B), supra.                                                     ______________________________________                                    

The ingredients are combined without the ground polymer and heated to75° C. These ingredients are mixed and continued to be heated until thesodium stearate has dissolved. The resulting mixture is cooled to 40° C.and the ground fragrance-containing polymer is added and mixed at 40° C.until the suspension is formed. The resulting suspension is cooled andformed into sticks and the deodorant sticks exhibit a pleasant, fresh,green, floral, rose aroma when utilized in the axillary areas of a humanbeing.

EXAMPLE XXII Herbal Perfune Formulation

The following mixtures are prepared:

    ______________________________________                                                       Parts by Weight                                                               EXAMPLES                                                       Ingredients      XXII(A)  XXII(B)   XXII(C)                                   ______________________________________                                        Oakmoss absolute (50% in                                                                       20       20        20                                        diethyl phthalate)                                                            Alpha-methyl-3,4-methylene-                                                                    10       10        10                                        dioxyhydrocinnamic aldehyde                                                   Methyl dihydrojasmonate                                                                        100      100       100                                       Courmarin        20       20        20                                        Musk ketone      80       80        80                                        Isocyclocitral (10% in                                                                         10       10        10                                        deithyl phthalate)                                                            Galbanum oil (10% in                                                                            6        6         6                                        Rosemary oil     10       10        10                                        Pine needle oil  60       60        60                                        Fir balsam absolute (10% in                                                                    10       10        10                                        diethyl phthalate)                                                            Bergamot oil     60       60        60                                        Lemon oil        14       14        14                                        Benzyl acetate   468      468       468                                       Linalool         80       80        80                                        Indole (10% in diethyl                                                                          6        6         6                                        phthalate)                                                                    Undecalactone (10% in                                                                          12       12        12                                        deithyl phthalate).                                                           2-Methyl-4-phenyl-1-pentanol                                                                   12        0         0                                        prepared according to U.S.                                                    Letters Patent 4,632,831.                                                     2-Methyl-4-phenyl-1-pentanol                                                                    0       20         0                                        acetate prepared according                                                    to U.S. Letters Patent                                                        4,632,831.                                                                    S(4-hydroxy-1-isopropyl-4                                                                      10       20        15                                        methylhexyl) thioacetate                                                      prepared according to                                                         Example II, supra.                                                            Mixture of S(4-hydroxy-1-                                                     isopropyl-4-methylhexyl)                                                      thioacetate having the                                                        structure:                                                                     ##STR140##                                                                   and               0        0         5                                        The compound having                                                           the structure:                                                                 ##STR141##                                                                   ______________________________________                                    

The addition to this herbal formulation of theS(4-hydroxy-1-isopropyl-4-methylhexyl) thioacetate imparts to thisherbal formulation excellent green, floral and rose undertones.Accordingly, the formulations of Examples XXII(A) and XXII(B) can bedescribed as "herbaceous, with green, floral and rose undertones".

The addition of the mixture of the compound having the structure:##STR142## and the compound having the structure: ##STR143## to thisherbal formulation imparts to the herbal formulation excellent green,floral, rose, natural "buchu leaf, tomato leaf, basil minty andgrapefruit-like topnotes and natural "ontiga", tomato leaf, minty andgrapefruit-like undertones. Accordingly, the formulation of ExampleXXII(C) can be described as "herbaceous with green, floral, rose,natural "buchu" leaf, tomato leaf, basil, minty and grapefruit-liketopnotes and natural "ontiga", tomato leaf, minty and grapefruit-like"undertones.

EXAMPLE XXIII Preparation of Cosmetic Powder Compositions

Cosmetic powder compositions are prepared by mixing in a ball mil 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table III below. Each of the cosmetic powder compositions hasan excellent aroma as described in Table III below.

                  TABLE III                                                       ______________________________________                                        Substance       Aroma Description                                             ______________________________________                                        S(4-hydroxy-1-isopropyl-                                                                      A green, floral, rose aroma                                   4-methylhexyl thioacetate                                                                     profile.                                                      having the structure:                                                          ##STR144##                                                                   Perfume composition                                                                           A herbaceous aroma with green,                                of Example XXII(A).                                                                           floral and rose undertones.                                   Perfume composition                                                                           A herbaceous aroma with green,                                of Example XXII(B).                                                                           floral and rose undertones.                                   Perfume composition                                                                           Herbaceous with green, floral,                                of Example XXII(C).                                                                           rose, natural "buchu" leaf,                                                   tomato leaf, basil, minty and                                                 grapefruit-like topnotes and                                                  natural "ontiga", tomato                                                      leaf, minty and grapefruit-                                                   like undertones.                                              ______________________________________                                    

EXAMPLE XXIV Perfumed Liquid Detergents

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No 3,948,818 issuedApr. 6, 1976 incorporated by reference herein) with aroma nuances as setforth in Table III of Example XXIII are prepared containing 0.10%,0.15%, 0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in TableIII of Example XXIII. They are prepared by adding and homogeneouslymixing the appropriate quantity of substance set forth in Table III ofExample XXIII in the liquid detergent. The detergents all possessexcellent aromas as set forth in Table III of Example XXIII, theintensity increasing with greater concentrations of substance as setforth in Table III of Example XXIII.

EXAMPLE XXV Preparation of Colognes and Handkerchief Perfumes

Compositions as set forth in Table III of Example XXIII are incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%and 5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions;and into handkerchief perfumes at concentrations of 15%, 20%, 25% and30% (in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table III ofExample XXIII are imparted to the colognes and to the handkerchiefperfumes at all levels indicated.

EXAMPLE XXVI Preparation of Soap Compositions

One hundred grams of soap chips (per sample)(IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table III of Example XXIIIuntil homogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under eight atmospheres pressure at180° C. for period of three hours and the resulting liquids are placedinto soap molds. The resulting soap cakes, on cooling, manifest aromasas set forth in Table III of Example XXIII.

EXAMPLE XXVII Preparation of Solid Detergent Compositions

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948 (incorporated by referenceherein):

    ______________________________________                                        Ingredient           Percent by Weight                                        ______________________________________                                        "NEODOL ® 45-11 (a C.sub.14 --C.sub.15                                                         12                                                       alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate     55                                                       Sodium citrate       20                                                       Sodium sulfate, water                                                                              q.s.                                                     brighteners                                                                   ______________________________________                                    

This detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table III of Example XXIII. Eachof the detergent samples has an excellent aroma as indicated in TableIII of Example XXIII.

EXAMPLE XXVIII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated herein by reference),nonwoven cloth substrates useful as drier-added fabric softeningarticles of manufacture are prepared wherein the substrate, thesubstrate coating, the outer coating and the perfuming material are asfollows:

1. A water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and a pH of3. An outer coating having the following formulation (m.p. about 150°F.):

    ______________________________________                                        57%         C.sub.20--22 HAPS                                                 22%         isopropyl alcohol                                                 20%         antistatic agent                                                   1%         of one of the substances as set forth in                                      Table III of Example XXIII.                                       ______________________________________                                    

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table III of Example XXIII, supra, consist of a substrate coatinghaving a weight of about 3 grams per 100 square inches of substrate; afirst coating located directly on the substrate coating consisting ofabout 1.85 grams per 100 square inches of substrate; and an outercoating coated on the first coating consisting of about 1.4 grams per100 square inches of substrate. One of the substances of Table III ofExample XXIII is admixed in each case with the outer coating mixture,thereby providing a total aromatized outer coating weight ratio tosubstrate of about 0.5:1 by weight of the substrate. The aromacharacteristics are imparted in a pleasant manner to the head space in adryer on operation thereof in each case using said drier-added fabricsoftener non-woven fabrics and these aroma characteristics are describedin Table III of Example XXIII, supra.

EXAMPLE XXIX Hair Spray Formulations

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 West51st Street, New York, N.Y., in 91.62 grams of 95% food grade ethanol.8.0 Grams of the polymer is dissolved in the alcohol. The followingingredients are to the PVP/VA alcoholic solution:

    ______________________________________                                                          Weight Percent                                              ______________________________________                                        Dioctyl sebacate    0.05                                                      Benzyl alcohol      0.10                                                      Dow Corning 473 fluid                                                                             0.10                                                      (prepared by the Dow Corning                                                  Corporation)                                                                  Tween 20 surfactant 0.03                                                      (prepared by ICI America                                                      Corporation)                                                                  One of the perfumery sub-                                                                         0.10                                                      stances as set forth in                                                       Table III of                                                                  Example XXIII, supra.                                                         ______________________________________                                    

The perfuming substances as set forth in Table III of Example XXIII addaroma characteristics as set forth in Table III of Example XXIII whichare rather intense and aesthetically pleasing to the users of thesoft-feel, good hold pump hair sprays.

EXAMPLE XXX Conditioning Shampoos

Monamid CMA (prepared by the Mona Industries Company)(3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation)(1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.). This material is "COMPOSITION A".

GAFQUAT® 755N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethylene glycol 6000distearate produced by Armak Corporation. This material is "COMPOSITIONB".

The resulting "COMPOSITION A" and "COMPOSITION B" are then mixed in a50:50 weight ratio of A:B and cooled to 45° C. and 0.3 weight percent ofperfuming substance as set forth in Table I of Example IV is added tothe mixture. The resulting mixture is cooled to 40° C. and blending iscarried out for an additional one hour in each case. At the end of thisblending period, the resulting material has a pleasant fragrance asindicated in Table III of Example XXIII.

What is claimed is:
 1. A cyano-substituted sulfur-containing compounddefined according to a structure selected from the group consisting of:##STR145## wherein M is an alkali metal.
 2. An organoleptically usefulmixture of cyano-substituted sulfur-containing compounds of claim 1defined according to the structures: ##STR146##
 3. A process foraugmenting or enhancing the aroma or taste of a consumable materialcomprising the step of adding to said consumable material, an aroma ortaste augmenting or enhancing quantity of the product defined accordingto claim
 1. 4. A process for augmenting or enhancing the aroma or tasteof a consumable material comprising the step of adding to saidconsumable material, an aroma or taste augmenting or enhancing quantityof the product defined according to claim 2.